EP4217410A1 - Wässrige selbstvernetzbare polyurethandispersionen - Google Patents

Wässrige selbstvernetzbare polyurethandispersionen

Info

Publication number
EP4217410A1
EP4217410A1 EP21778371.1A EP21778371A EP4217410A1 EP 4217410 A1 EP4217410 A1 EP 4217410A1 EP 21778371 A EP21778371 A EP 21778371A EP 4217410 A1 EP4217410 A1 EP 4217410A1
Authority
EP
European Patent Office
Prior art keywords
group
carrying
weight
polyurethane
keto
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21778371.1A
Other languages
English (en)
French (fr)
Inventor
Samane MEHRAVAR
Paola Uribe Arocha
Daniel VON NESSEN
Konrad Roschmann
Florian Ludwig GEYER
Mo Kit CHAU
Florian Schluetter
Juergen Kaczun
David TUERP
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP4217410A1 publication Critical patent/EP4217410A1/de
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C08G18/4241—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols from dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4291—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from polyester forming components containing monoepoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C08K5/25—Carboxylic acid hydrazides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D15/00—Woodstains
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • Aqueous self-crosslinkable polyurethane coating composition in particular those for coating interior wood substrates such as parquet flooring, ideally contain only a low amount of organic solvent, and are able to crosslink at low temperatures such as room temperature without addition of an external crosslinker under formation of a homogeneous crack-free film.
  • Aqueous self-crosslinkable polyurethane coating composition are known in the art.
  • US4983662 describes an aqueous self-crosslinkable coating composition suitable for coating wood, metal, fabrics and plastics comprising an aqueous dispersion which comprises at least one polyurethane polymer, wherein said composition has hydrazine (or hydrazone) functional groups and carbonyl functional groups present in the composition to provide a selfcrosslinking reaction, in which said at least polyurethane polymer takes part, via azomethine formation from the reaction of hydrazine (or hydrazone) functional groups and carbonyl functional groups during and/or after film formation from the aqueous composition of at least one polyurethane.
  • the polyurethane bears chain-pendant carbonyl functional groups and the composition includes a non-polyurethanic, non-vinylic polyhydrazine compound.
  • Example 1 describes an aqueous self-crosslinkable coating composition containing polytetrahydrofuran- based polyurethane having pendant carbonyl-functional groups formed from dihydroxyacetone, as well as adipic acid dihydrazide and an acrylic copolymer.
  • Example 2 describes an aqueousbased self-crosslinkable coating composition containing a polytetrahydrofuran-based polyurethane having pendant carbonyl-functional groups formed from the adduct of diethanolamine with diacetoneacrylamide, as well as adipic acid dihydrazide (ADDH).
  • a polytetrahydrofuran-based polyurethane having pendant carbonyl-functional groups formed from the adduct of diethanolamine with diacetoneacrylamide, as well as adipic acid dihydrazide (ADDH).
  • US20070093594 describes self-crosslinkable aqueous polyurethane dispersions containing a crosslinking agent selected from diamines and dihydrazides, and polyurethanes containing a carbonyl group derived from compound F.
  • Compound F contains at least one group which is reactive towards isocyanate and at least one aldehyde-type or ketone-type carbonyl group.
  • W02006086322 describes an aqueous dispersion of polyurethane including co-reactive mole- cules/oligomers of a) a ketone functional moiety/molecule and b) a hydrazine functional moiety useful in a variety of applications including coatings such as wood floor coatings.
  • ketone functional molecules are i) the product of bisphenol A diglycidyl ether and levulinic acid, (example A) and the product of bisphenol A diglycidyl ether, levulinic acid, benzyl benzoate and 1 ,6-hexane diisocyanate (example B), and the product of 1 ,1 ,1-tris(hydroxymethyl) propane, levulinic acid and isophorone diisocyanate (example D).
  • W02008016843 describes an aqueous dispersion of polyurethane including co-reactive mole- cules/oligomers of a) a ketone functional moiety/molecule and b) a hydrazine functional moiety useful in a variety of applications including coatings such as wood floor coatings.
  • a preferred ketone molecule is the reaction product of levulinic acid with epoxides of linseed or soybean oil.
  • the ketone functional moieties are introduced into the reaction mixture at any time during polyurethane prepolymer or polyurethane formation when they can be uniformely dispered, in one embodiment this is before the prepolymer is dispersed in water.
  • Exemplified dispersion 2 is an aqueous dispersion containing a polyester-based polyurethane, a ketone-functional molecule derived from levulinic acid and epoxidized lineseed oil, and adipic acid dihydrazide (ADDH).
  • the dispersion is suitable for wood floor coating.
  • W02009105400 describes aqueous polyurethane dispersions made from urethane prepolymers comprising one or more polyhydroxy compounds from ketone functional molecules derived from epoxidized natural oil. Addition of a hydrazine functional moiety to the prepolymer dispersion can provide crosslinking in the formation of azomethine linkages in the resulting polyurethane during drying.
  • the polyhydroxy compound can be a ketone-functional molecule derived from levulinic acid and epoxidized vegetable oil.
  • the dispersions are suitable for wood flooring.
  • WO2013153093 describes a process for preparing Schiff-base crosslinkable aqueous polyurethane dispersions, which does not involve the use of volatile amines.
  • Example 1 describes an aqueous polyurethane acrylic hybrid dispersion, wherein the polyurethane comprises a keto polyesterpolyol as synthesis component, and adipic acid dihydrazide.
  • WO2015030955 describes aqueous dispersions of a self-crosslinkable polymer comprising urethane as well as hydrazide units.
  • the linking group L 1 can be any linking group.
  • Levulinic acid can be prepared from renewable materials such as hexoses, e.g. glucose or fructose, or from starch by methods known in the art.
  • Ci-io-alkylene and Ci-6-alkylene can be branched or unbrached. Examples of Ci-6-alkylene are methylene, ethylene, propylene, 1 -methylethylene, butylene, 1 ,1 -dimethylethylene, pentylene and hexylene.
  • Ci- -alkylene examples include methylene, ethylene, propylene, 1-methyl- ethylene, butylene, 1 ,1 -dimethylethylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene.
  • Cs-s-cycloalkyl examples include cyclopentyl and cyclohexyl.
  • Ce- -aryl examples are phenyl and naphthyl.
  • C?-2o-aralkyl examples include benzyl, (2-phenyl)ethyl and (3-phenyl)n-propyl.
  • Ci-4-alkyl, Ci-e-alkyl, Ci- -alkyl and Ci-2o-alkyl can be branched or unbrached.
  • Examples of C1.4- alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl .
  • Ci- 6-alkyl examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl tert-butyl, pentyl, 2-pentyl, 3- pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, hexyl, 2-hexyl and 3-hexyl.
  • Ci-w-alkyl examples are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2- pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, hexyl, 2-hexyl, 3-hexyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl.
  • Ci-2o-alkyl examples are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2- dimethylpropyl, hexyl, 2-hexyl, 3-hexyl heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
  • the polyester polyol (1) has preferably a number average molecular weight Mn in the range of 500 to 10000 g/mol, more preferably of 1000 to 6000 g/mol, even more preferably from 1500 to 4000 g/mol, and most preferably from 1500 to 3500 g/mol.
  • the number average molecular weight Mn is determined using gel permeation chromatography calibrated to a polystyrene standard.
  • the polyester polyol (1) has preferably a dispersity D determined by dividing the weight average molecular weight Mw by the number average molecular weight Mn, of 1-40, more preferably of 1-20, even more preferably of 1-15 and most preferably of 1-10.
  • the weight average molecular weight Mw and the number average molecular weight are determined using gel permeation chromatography calibrated to a polystyrene standard.
  • the polyester polyol (1) has an acid number below 10 mg KOH/g, more preferably below 5 mg KOH/g, even more preferably below 4.5 mg KOH/g, most preferably in the range of 1.5 to 4 mg KOH/g.
  • the acid number is determined according to DIN53402, 1990.
  • the polyester polyol (1) has a hyroxyl number of 20-300 mg KOH/g, more preferably of 30-250 mg KOH/g, even more preferably of 40-200 mg KOH/g, most preferably of 50-150 mg KOH/g.
  • the polyester polyol (1) has an average OH-functionality of 2 to 10, more preferably from 2.2 to 8, even more preferably from 2.4 to 6, and most preferably from 2.5 to 4.5.
  • OH-functionality refers to the number of OH-groups carried by one polyester polyol molecule.
  • the polyester polyol (1) comprises units derived from
  • L 1 is a linking group
  • R 1 is selected from the group consisting of Ci-20-alkyl, Cs-s-cycloalkyl, Ce- -aryl and C?-2o-aralkyl, at least one diacid (1 ii) or derivative thereof, optionally at least one polyacid (1 iii) carrying at least three COOH groups or derivative thereof, at least one diol (1 iv), at least one polyol (1v) carrying at least three OH groups, and optionally at least one compound (1 vi) comprising at least one epoxy group.
  • the polyester polyol (1) comprises units derived from
  • the polyester polyol (1) consists of units derived from
  • polyester polyol (1) consists of units derived from
  • the molar ratio of the sum of OH groups of (1 iv) and (1 v) to the sum of COOH groups of (1 i) or derived from a derivative thereof, of (1 ii) or derived from a derivative thereof and of (1 iii) or derived from a derivative thereof is in the range of 0.8/1 to 1 .6/1 , preferably in the range of 0.9/1 to 1.4/1 , more preferably in the range of 1/1 to 1.3/1.
  • Aromatic diacids carry two COOH groups, wherein at least one COOH group is directly attached to an aromatic ring.
  • Alicyclic diacids carry two COOH groups and comprise at least one alicyclic ring and wherein each COOH group is not directly attached to an aromatic ring.
  • Aliphatic diacids carry two COOH groups and comprise no alicyclic ring, and each COOH group is not directly attached to an aromatic ring.
  • Preferred aliphatic, alicyclic and aromatic diacids exclusively consist, apart from the two COOH groups, of carbons and hydrogens.
  • Derivatives of the diacid (1 ii) can be the corresponding anhydride in monomeric or polymeric form, the corresponding mono- or di-Ci-4-alkyl-esters such as monomethyl ester, dimethyl ester, monoethylester, diethyl ester or mixed methyl ethyl esters, the corresponding amides, or the corresponding acid halides such as chlorides or bromides.
  • aliphatic diacids examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelinic acid, suberic acid, azelaic acid, sebacic acid, 1 ,11 -undecanedicarboxylic acid, 1 ,12-dodecanedicarboxlyic acid, maleic acid, fumaric acid, 2-methylmalonic acid, 2-ethylmalonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, itaconic acid, 3,3-dimethylglutaric, 2-phenyl- malonic acid and 2-phenylsuccinic acid.
  • alicyclic diacids examples include cyclopentane-1,2-dicarboxylic acid, cyclopentane- 1,3- dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1 ,3-dicarboxylic acid, cyclo- hexane-1 ,4-dicarboxylic acid, cycloheptane-1,2-dicarboxylic acid, 1 ,2-bis(carboxymethyl)- cyclohexane, 1,3-bis(carboxymethyl)-cyclohexane and 1 ,4-bis(carboxymethyl)-cyclohexane.
  • aromatic diacids examples include phthalic acid, isophthalic acid, terephthalic acid and bis(4- carboxyphenyl) methane.
  • the diacid (1 ii) is an aliphatic or alicyclic diacid. More preferably, the diacid (1 ii) is and aliphatic diacid. Even more preferably, the diacid (1 ii) is an aliphatic diacid selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, pimelinic acid, suberic acid and azelaic acid. Most preferably, the diacid (1 ii) is adipic acid.
  • the polyacid (1 iii) carrying at least three COOH groups can be an aliphatic, alicyclic or aromatic polyacid carrying at least three COOH groups.
  • Examples of alicyclic polyacids carrying three COOH groups are 1,3,5-cyclohexanetricarboxylic acid and aconitic acid.
  • Examples of aromatic polyacid carrying three COOH groups are 1 ,2,4- benzenetricarbocxylic acid and 1 ,3,5-benzenetricarbocxylic acid.
  • An example of an aromatic polyacid carrying four COOH groups is 1,2,4,5-benzenetetracarboxylic acid.
  • An example of an aromatic polyacid carrying six COOH groups is mellitic acid.
  • Derivatives of the polyacid carrying at least 3 COOH groups (1 iii) can be the corresponding anhydride in monomeric or polymeric form, the corresponding mono- or di-Ci-4-alkyl-esters such as monomethyl ester, dimethyl ester, monoethylester, diethyl ester or mixed methyl ethyl esters, the corresponding amides, or the corresponding acid halides such as chlorides or bromides.
  • An example of a derivative of a polyacid carrying at least three COOH groups (1 iii) is pyromellitic dianhydride.
  • the diol (1 iv) can be an aliphatic, alicyclic or aromatic diol.
  • Aromatic diols carry two OH groups, wherein at least one OH group is directly attached to an aromatic ring.
  • Alicyclic diols carry two OH groups and comprise at least one alicyclic ring and wherein each OH group is not directly attached to an aromatic ring.
  • Aliphatic diols carry two OH groups and comprise no alicyclic ring, and each OH group is not directly attached to an aromatic ring.
  • Preferred aliphatic, alicyclic and aromatic diols exclusively consist, apart from the two OH groups, of carbons and hydrogens.
  • Preferred aliphatic and alicyclic diols exclusively consist, apart from the two OH groups, of carbons and hydrogens, and do not comprise an aromatic ring.
  • aliphatic diols are ethylene glycol, propane-1 , 2-diol, propane-1 , 3-diol, butane-1 ,2- diol, butane-1 , 3-diol, butane-1 ,4-diol, butane-2, 3-diol, pentane-1 , 2-diol, pentane-1 , 3-diol, pen- tane-1 , 4-diol, pentane-1 , 5-diol, pentane-2, 3-diol, pentane-2,4-diol, hexane-1 , 2-diol, hexane-1 , 3- diol, hexane-1 , 4-diol, hexane-1 , 5-diol, hexane-1 , 6-diol, hexane-2, 5-diol, heptane-1 , 2-dio
  • alicyclic diols examples include 1 ,1-bis(hydroxymethyl)-cyclohexane, 1 ,2-bis(hydroxymethyl)- cyclohexane, 1 ,3-bis(hydroxymethyl)-cyclohexane, 1 ,4-bis(hydroxymethyl)-cyclohexane, 1 ,1- bis(hydroxyethyl)-cyclohexane, 1 ,2-bis(hydroxyethyl)-cyclohexane, 1 ,3-bis(hydroxyethyl)-cyclo- hexan, 1 ,4-bis(hydroxyethyl)-cyclohexane, 2,2,4,4-tetramethyl-1 ,3-cyclobutandiol, cyclopen- tane-1 , 2-diol, cyclopentane- 1 , 3-diol, 1 ,2-bis(hydroxymethyl) cyclopentane, 1 ,3- bis(hydroxymethyl) cyclopentane,
  • the diol (1 iv) is an aliphatic or alicyclic diol. More preferably, the diol (1 iv) is an alicyclic diol. Even more preferably, the diol (1 iv) is an alicyclic diol dselected from the group consisting of 1 ,1-bis(hydroxymethyl)-cyclohexane, 1,2-bis(hydroxymethyl)-cyclohexane, 1,3-bis- (hydroxymethyl)-cyclohexane, 1 ,4-bis(hydroxymethyl)-cyclohexane, 1 ,1-bis(hydroxyethyl)- cyclohexane, 1,2-bis(hydroxyethyl)-cyclohexane, 1,3-bis(hydroxyethyl)-cyclohexan and 1,4- bis(hydroxyethyl)-cyclohexane. Most preferably, the diol (1 iv) is 1,4-bis(hydroxymethyl)- cyclo
  • the polyol carrying at least three OH groups (1v) can be an aliphatic, alicyclic or aromatic polyol carrying at least three OH groups.
  • Aromatic polyols carrying at least three OH groups carry at least one OH group which is directly attached to an aromatic ring.
  • Alicyclic polyols carrying at least three OH groups comprise at least one alicyclic ring and each OH group is not directly attached to an aromatic ring.
  • Aliphatic polyols carrying at least three OH groups comprise no alicyclic ring, and each OH group is not directly attached to an aromatic ring.
  • Preferred aliphatic and alicyclic polyols carrying at least three OH groups do not comprise aromatic rings. More preferred aliphatic and alicyclic polyols carrying at least three OH groups do not comprise aromatic rings and, exclusively consist, apart from the the OH groups, of carbons and hydrogens.
  • Examples of aliphatic polyols carrying at least three OH groups are glycerol, trimethylolmethane, 1,1 ,1 -trimethylolethane, 1 ,1 ,1 -trimethylolpropane, 1 ,2,4-butanetriol, pentaerythritol, 1,3,5- tris(2-hydroxyethyl)isocyanurate, diglycerol, triglycerole, condensates of at least four glycerols, di(trimethylolpropane) and di (pentaerythritol, and condensates of aliphatic compounds carrying at least three OH groups with ethylene oxide, propylene oxide and/or butylene oxide.
  • alicyclic polyols carrying at least three OH groups are inositol, sugars such as glucose, fructose and sucrose, sugar alcohols such as sorbitol, mannitol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), malitol and isomalt, as well as tris(hydroxymethyl)amine, tris(hydroxyethyl)amine and tris(hydroxypropyl)amine.
  • sugars such as glucose, fructose and sucrose
  • sugar alcohols such as sorbitol, mannitol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), malitol and isomalt, as well
  • the polyol (1v) carrying at least three OH groups is an aliphatic or alicyclic polyol carrying at least three OH groups. More preferably, the polyol (1v) carrying at least three OH groups is an aliphatic polyol carrying at least three OH groups. Even more preferably, the polyol carrying at least three OH groups is an aliphatic polyol carrying at least three OH groups selected from the group consisting of trimethylolmethane, 1 ,1,1 -trimethylolethane, 1,1 ,1- trimethylolpropane and 1 ,2,4-butanetriol. Most preferably, the polyol carrying at least three OH groups is 1 ,1 ,1 -trimethylolpropane.
  • the compound (1 vi) carrying at least one epoxy group can be a compound carrying one epoxy group or compounds carrying ate least two epoxy groups.
  • Examples of compounds carrying one epoxy group are glycidyl ester of a Ce-20-alkanoic acid, preferably of a Cg-n-akanoic acids, wherein the alpha-carbon is a quaternary carbon atom, such neodecanoic acid, 2,3-epoxypropyl ester.
  • Examples of compounds carrying two epoxy group bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, 1 ,4-butandiol diglycidylether and pentaerythritol tetraglycidylether.
  • the compound (1 vi) carrying at least one epoxy group is preferably, a compound carrying one epoxy group, more preferably the glycidyl ester a Cg-n-akanoic acids, wherein the alpha-carbon is a quaternary carbon atom.
  • the esterification reaction is performed in the presence of a catalyst.
  • the catalyst can be selected from the group consisting of acidic inorganic catalysts, acidic organic catalysts, organometallic catalysts and mixtures thereof.
  • acidic organic catalysts examples include organic compounds containing phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups, such as para-toluene sulfonic acid and methane sulfonic acid.
  • acidic organic catalysts are acidic ion exchangers such as polystyrene resins being crosslinked with divinylbenzene and containing sulfonic acid groups.
  • organometallic catalysts are organic aluminium catalysts such as tris(n- butyloxy)aluminium, tris(isopropyloxy)aluminium and tris(2-ethylhexoxy)aluminium, as well as organic titanium catalysts such as titanium(IV) butoxide, tetra(isopropyloxy)titanium (IV) and tetra(2-ethylhexoxy)titanium(IV), organic tin catalysts such as dibutyltin oxide, diphenyltin oxide, dibutyltin dichloride, tin(ll)di(n-octanoate), tin(ll) di(2-ethylhexanoate), tin(ll) laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate and dioctyltin diacetate as well as organic zinc catalysts such as zinc
  • the catalyst is an organometallic catalyst, more preferably an organic titanium catalyst, most preferably titanium (IV) butoxide.
  • solvents examples include hydrocarbons such as n-heptane, cyclohexene, toluene, ortho-xylene, meta-xylene, para-xylene, xylene isomer mixture, ethylbenzene, chlorobenzene, ortho- and meta-dichlorobenzene.
  • ethers such as dioxane or tetrahydrofuran
  • ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • the amount of solvent, if present at all, is below 5 weight% based on the weight of the reaction mixture of the esterification step.
  • Water formed in the course of the esterification step can be removed continuously during the reaction, for example by distillation. Water can also be removed by stripping or by performing the reaction in the presence of a water-removing agent such as MgSC and Na2SO4. Preferably, water is removed by distillation, optionally in combination with other water- rem ova I methods. If other volatile components, for example methanol or ethanol, are formed in the course of the reaction, these can also be removed, for example by distillation or stripping.
  • a water-removing agent such as MgSC and Na2SO4.
  • water is removed by distillation, optionally in combination with other water- rem ova I methods. If other volatile components, for example methanol or ethanol, are formed in the course of the reaction, these can also be removed, for example by distillation or stripping.
  • the esterification reaction is carried out under a gas, which is inert under the reaction conditions.
  • Suitable inert gases include nitrogen and argon.
  • the esterification reaction can be performed at a pressure in the range of 10 mbar to 10 000 mbar, preferably at a pressure in the range of 10 to 2000 mbar, more preferably at a pressure in the range of 10 to 1200 mbar, most preferably at a pressure in the range of 100 to 1100 mbar.
  • the temperature used in the esterification step is usully in the range of 60 to 250 °C, preferably, in the range of 100 to 240 °C and more preferably in the range of 120 to 220 °C.
  • the esterification reaction can be monitored by determining the hydroxyl number or acid number of the product of the esterifying step.
  • the compound (1 vi) carrying at least one epoxy group is can be added.
  • the reaction of the second step can proceed at a temperature of 150 to 250 °C.
  • the polyester polyol (1) obtained can be worked-up by methods known in the art or used as “crude” product.
  • the aqueous polyurethane dispersion (PUD) of the present invention comprises
  • the aqueous polyurethane dispersion (PUD) of the present invention consists of
  • SC-PUD self-crosslinkable polyurethane dispersion
  • the aqueous self-crosslinkable polyurethane dispersion (SC-PUD) of the present invention preferably comprises
  • the aqueous self-crosslinkable polyurethane dispersion (SC-PUD) of the present invention comprises
  • the aqueous self-crosslinkable polyurethane dispersion (SC-PUD) of the present invention comprises
  • the aqueous self-crosslinkable polyurethane dispersion (SC-PUD) of the present invention consists of
  • the solid content of the aqueous self-crosslinkable polyurethane dispersion (SC-PUD) comprising the polyurethane (2) is usually in the range of 10 to 80 weight%, preferably 20 to 60 weight%, more preferably 25 to 50 weight%.
  • the solid content is determined using DIN ISO 3251 ,2019
  • the aqueous self-crosslinkable polyurethane dispersion (SC-PUD) comprising the polyurethane (2) has usually a viscosity at 23 °C in the range of 10 to 1000 mPas, preferably in the range of 30 to 500 mPas, most preferably in the range of 50 to 300 mPas.
  • the viscosity is determined using DIN ISO 2555,2018.
  • the aqueous self-crosslinkable polyurethane (SC-PUD) dispersion comprising the polyurethane (2) has usually a pH in the range of 7 to 9.
  • the pH is determined using DIN ISO 976, 2016.
  • the aqueous self-crosslinkable polyurethane dispersion (SC-PUD) comprising the polyurethane (2) has usually a minimum film forming temperature in the range of 1 to 50 °C, preferably in the range of 5 to 25 °C.
  • the minimum film forming temperature is determined using DIN ISO 2115, 2001.
  • the particles of the aqueous self-crosslinkable polyurethane dispersion (SC-PUD) comprising the polyurethane (2) have usually an average particle size of 10 nm to 5000, preferably from 10 nm to 1000 nm, more preferably from 20 nm to 500 nm, most preferably from 20 to 200 nm.
  • the average particle size is determined using dynamic light scattering (DLS) ISO 22412, 2017.
  • the molar ratio of the NCO groups of (2v) to the sum of OH groups of (1), (2i), (2ii) (2iii) and (2iv) is preferably in the range of 0.9/1 to 1.6/1 , more preferably in the range of from 1/1 to 1.4/1, most preferably in the range of 1.1/1 to 1.3/1.
  • the molar ratio of the NCO groups of (2v) to the sum of amino groups independently selected from the group consisting of primary and secondary amino groups of (2vi) is preferably in the range of 2/1 to 20/1, more preferably in the range of from 4/1 to 16/1, most preferably in the range of 7/1 to 14/1.
  • the molar ratio of the NCO groups of (2v) to the sum of OH groups of (1), (2i), (2ii) (2iii) and (2iv) and amino groups independently selected from the group consisting of primary and secondary amino groups of (2vi) is preferably in the range of 0.8/1 to 1.3/1, more preferably in the range of from 0.9/1 to 1.2/1, most preferably in the range of 1/1 to 1.1/1.
  • the weight ratio of the sum of (1), (2i) (2ii), (2iii), (2iv), (2v) and (2vi) to (2vii) is preferably in the range of from 50/50 to 10/90.
  • the polymeric polyol (2i) different from polyester polyol (1) can be any polymeric polyol.
  • polymeric polyols (2i) are polyester polyols, polyether polyols, polycarbonate polyol, poly(meth)acrylate polyols, polyurethane polyols, a poly(urea-formaldehyde) polyols, poly(melamine-formaldehyde) polyols, natural oil polyols, polybutadiene polyols, polysulfide polyols.
  • the polymeric polyol (2i) is selected from the group consisting of a polyester polyol polyether polyol and polycarbonate polyol. More preferably, the polymeric polyol (2i) is a polyester polyol. Most preferably, the polymeric polyol (2i) is a polyester polyol comprising units derived from an aliphatic diacid or a derivative thereof, an aromatic diacid or a derivative thereof and an aliphatic diol. Aliphatic diacids and derivatives thereof, aromatic diacids and derivatives thereof and aliphatic diols are as defined above.
  • the polymeric polyol (2i) has an number average molecular weight of from 500 to 10000 g/mol, more preferably of from 600 to 8000 g/mol, even more preferably of from 800 to 5000 g/mol, and most preferably of from 1000 to 3000 g/mol.
  • the number average molecular weight is determined by gel permeation chromatography using polystyrene standards.
  • the polymeric polyol (2i) has an average OH-functionality of 1.5 to 8, more preferably from 1.6 to 6, even more preferably from 1.7 to 4, and most preferably from 1.8 to 2.5.
  • the polymeric polyol (2i) has an OH-number of from 10 to 200 mg KOH/g, more preferably of from 20 to 100 mg KOH/g.
  • the OH number is determined using DIN53240, 2016.
  • the polyol (2ii) having a molecular weight of below 400 g/mol can be a diol having a molecular weight of below 400 g/mol or a polyol carrying at least 3 OH groups and having a molecular weight of below 400 g/mol.
  • the diol having a molecular weight of below 400 g/mol can be an aliphatic, alicyclic or aromatic diol having a molecular weight of below 400 g/mol.
  • Aliphatic, alicyclic or aromatic diols are defined above.
  • Examples of aliphatic diols having a molecular weight of below 400 g/mol are ethylene glycol, propane-1, 2-diol, propane-1 , 3-diol, butane-1 ,2-diol, butane-1,3-diol, butane-1,4-diol, butane-2,3- diol, pentane-1 , 2-diol, pentane-1, 3-diol, pentane-1,4-diol, pentane-1,5-diol, pentane-2, 3-diol, pentane-2,4-diol, hexane-1, 2-diol, hexane-1, 3-diol, hexane-1,4-diol, hexane-1,5-diol, hexane- 1 ,6-diol, hexane-2,5-dio
  • aliphatic diols having a molecular weight of below 400 g/mol are diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols, polypropylene glycols, polyethylene-polypropylene glycols, the sequence of the ethylene oxide or propylene oxide units being blockwise or random, polytetramethyleneglycols, polytetrahydrofurane and polycaprolactone, all having a molecular weight of below 400 g/mol.
  • Examples of alicyclic diols having a molecular weight of below 400 g/mol are 1 ,1- bis(hydroxymethyl)-cyclohexane, 1 ,2-bis(hydroxymethyl)-cyclohexane, 1 ,3-bis(hydroxymethyl)- cyclohexane, 1,4-bis(hydroxymethyl)-cyclohexane, 1,1-bis(hydroxyethyl)-cyclohexane, 1,2- bis(hydroxyethyl)-cyclohexane, 1 ,3-bis(hydroxyethyl)-cyclohexan, 1 ,4-bis(hydroxyethyl)- cyclohexane, 2,2,4,4-tetramethyl-1 ,3-cyclobutandiol, cyclopentane-1,2-diol, cyclopentane-1 ,3- diol, 1 ,2-bis(hydroxymethyl) cyclopentane, 1,3-bis(hydroxymethyl) cyclopentan
  • An example of an aromatic diol is benzene-1 ,2-diol.
  • the polyol carrying at least 3 OH groups and having a molecular weight of below 400 g/mol can be an aliphatic, alicyclic or aromatic polyol carrying at least 3 OH groups and having a molecular weight of below 400 g/mol.
  • Aliphatic, alicyclic or aromatic polyol carrying at least 3 OH groups are as defined above.
  • Examples of aliphatic polyols carrying at least three OH groups and having a molecular weight of below 400 g/mol are glycerol, trimethylolmethane, 1 ,1,1 -trimethylolethane, 1 ,1 ,1- trimethylolpropane, 1 ,2,4-butanetriol, pentaerythritol, 1 ,3,5-tris(2-hydroxyethyl)isocyanurate, diglycerol, triglycerole, condensates of at least four glycerols, di(trimethylolpropane) and di(pentaerythritol, and condensates of aliphatic compounds carrying at least three OH groups with ethylene oxide, propylene oxide and/or butylene oxide.
  • Examples of alicyclic polyols carrying at least three OH groups and having a molecular weight of below 400 g/mol are inositol, sugars such as glucose, fructose and sucrose, sugar alcohols such as sorbitol, mannitol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), malitol and isomalt, as well as tris(hydroxymethyl)amine, tris(hydroxyethyl)amine and tris(hydroxypropyl)amine.
  • sugars such as glucose, fructose and sucrose
  • sugar alcohols such as sorbitol, mannitol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (gal
  • the polyol (2ii) is a diol having a molecular weight of below 400 g/mol. More preferably, the polyol (2ii) is an aliphatic diol having a molecular weight of below 400 g/mol.
  • the polyol (2ii) is an aliphatic diol having a molecular weight of below 400 g/mol selected from the group consisting of are ethylene glycol, propane-1, 2-diol, propane-1 , 3-diol, bu- tane-1, 2-diol, butane-1, 3-diol, butane-1 ,4-diol, butane-2, 3-diol, pentane-1 , 2-diol, pentane-1, 3- diol, pentane-1, 4-diol, pentane-1, 5-diol, pentane-2, 3-diol, pentane-2,4-diol, hexane-1, 2-diol, hexane-1, 3-diol, hexane-1 ,4-diol, hexane-1, 5-diol, hexane-1, 6-dio
  • the polyol (2ii) is butane-1 , 4-diol.
  • the polyol (2iii) carrying at least one acidic group or a salt thereof can be a diol carrying at least one acidic group or salt thereof or a polyol carrying at least three OH groups and at least one acidic group or salt thereof.
  • Salts thereof are any salts thereof formed by treatment of the at least one acidic group with a base.
  • the base is used in an amount that in the range of from 50 to 95%, more preferably of from 65 to 90% of all acidic groups are reacted to the salt thereof.
  • the base can be an inorganic base, ammonia or an amine carrying only one amino group.
  • the base is preferably used in amounts that in the range of from 50 to 95%, more preferably in the range of fron 60 to 90% if all acidic groups are converted to the salt thereof.
  • inorganic bases are alkali and alkaline earth metal hydroxide, alkali and alkaline earth metal carbonate as well as alkali and alkaline earth metal hydrogencarbonate.
  • Preferred inorganic bases are alkali metal hydroxide such as sodium or potassium hydroxide, alkali metal carbonate such as sodium carbonate and potassium carbonate as well as alkali metal hydrogencarbonate such as sodium hydrogen carbonate and potassium hydrogen carbonate.
  • the amino group of the amine carrying only one amino group can be a primary, secondary or tertiary amino group.
  • amines carrying only one primary amino group are n-butylamine, n-hexylamine, 2- ethyl-1 -hexylamine, ethanolamine, 3-methoxypropylamine, 2-(2-aminoethyoxy)ethanol, 2- amino-1 -propanol, 3-amino-propanol, 2-amino-butan-1-ol, benzylamine, 1-(3-aminopropyl) imidazole, tetrahydrofurfurylamine, cyclohexylamine
  • Examples of amine carrying only one secondary amino group are dimethylamine, diethylamine, diisopropylamine, di-n-butylamine, diethanolamine, dipropanolamine, piperidine, pyrrolidine and morpholine.
  • Examples amines carrying only one tertiary amino group are triethanolamine, tripropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, dimethylethanolamine, diethylethanolamine, triethylamine, ethyldiisopriopylamine, tripropylamine, triisopropylamine and tri-n-butylamine.
  • diols carrying at least one acidic group or salt thereof are 2,2-bis(hydroxymethyl) C2-io-alkanoic acids or salts thereof such as 2,2-bis(hydroxymethyl) acetic acid, 2,2-bis(hydroxy- methyl) propionic acid (dimethylolpropionic acid), 2,2-bis(hydroxymethyl) butanoic acid, 2,2- bis(hydroxymethyl) pentanoic acid or salts thereof.
  • the polyol (2ii) carrying at least one acidic group or a salt thereof is preferably a diol carrying at least one acidic group or salt thereof, more preferably, a 2,2-bis(hydroxymethyl) C2-io-alkanoic acid or a salt thereof, even more preferably 2,2-bis(hydroxymethyl) propionic acid (dimethylolpropionic acid) or 2,2-bis(hydroxymethyl) butanoic acid or a salt thereof formed by treatment of the acidic group with an amine carrying only one amino group, and most preferably 2,2- bis(hydroxymethyl) propionic acid (dimethylolpropionic acid) or a salt thereof formed by treatment with an amine carrying only one teriary amino group.
  • the alcohol or polyol (2iv) carrying at least one olefinically unsaturated group can by any alcohol or polyol carrying at least one olefinically unsaturated group.
  • Alcohols carry only one OH group.
  • Polyols carry at least two OH groups
  • the alcohol carrying at least one olefinically unsaturated group can be an alcohol carrying one olefinically unsaturated group or an alcohol carrying at least two olefinically unsaturated groups.
  • the alcohols carrying one ethylenically unsaturated group are the partial esterification products carrying one OH group of the diol (1 iv) described above with (meth)acrylic acid.
  • Examples of alcohols carrying at one ethylenically unsaturated group are hydroxy Ci- -alkyl (meth)acrylates such as hydroxymethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl- (meth)acrylate and 4-hydroxybutyl(meth)acrylate.
  • Examples of alcohols carrying at least two ethylenically unsaturated group are the partial esterification products carrying one OH group of the polyol (1v) described above with (meth)acrylic acid.
  • Examples of alcohols carrying at at least two ethylenically unsaturated group are pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate and dipentaerythritol pen- ta(meth)acrylate.
  • polyols carrying at least one ethylenically unsaturated group are the partial esterification products carrying at least two OH groups of the polyol carrying at least three OH groups (1v) mentioned above with (meth)acrylic acid.
  • polyols carrying at least one ethylenically unsaturated group are the partial esterification products carrying at least two OH groups of an ethoxylated or polyethoxylated 1 ,1 ,1 -trimethylolpropane with meth(acrylic acid), dipentaerythritol tri(meth)acrylate and dipentaerythritol tetra(meth)acrylate.
  • (Meth)acrylic acid include methacrylic and acrylic acid.
  • the alcohol or polyol (2iv) carrying at least one ethylenically unsaturated group is preferably an alcohol carrying at least one ethylenically unsaturated group, more preferably an alcohol carrying one ethylenically unsaturated group, even more preferably hydroxy Ci- -alkyl (meth)acrylate, and most preferably 2-hydroxyethyl (meth)acrylate.
  • the polyisocyanate (2v) can be an aliphatic, alicyclic or aromatic polyisocyanate.
  • the NCO functionality of the polyisocyanate is in the range of from 1.8 to 10, more preferably in the range of 1 .9 to 4, most preferably in the range of 1 .9 to 2.5.
  • Aromatic polyisocyanates are polyisocyanates, wherein at least one NCO group is directly attached to an aromatic ring. Alicyclic polyisocyanates comprise at least one alicyclic ring and each NCO group is not directly attached to an aromatic ring. Aliphatic polyisocyanates do not comprise an alicyclic ring and each NCO group is not directly attached to an aromatic ring. Preferred aliphatic and alicyclic polyisocyanates do not comprise aromatic rings.
  • the NCO groups of the polyiscyanate can be blocked or, preferably, unblocked.
  • the polyisocyanate (2v) can be a monomeric polyisocyanate or polymeric polyisocyanate.
  • Examples of monomeric aliphatic polyisocyanates carrying two NCO groups are tetramethylene 1 ,4-diisocyanate, pentamethylene 1 ,5-diisocyanate, hexamethylene 1 ,6-diisocyanate, octamethylene 1 ,8-diisocyanate, decamethylene 1 ,10-diisocyanate, dodecamethylene 1 ,12- diisocyanate, tetradecamethylene 1 ,14-diisocyanate, methyl 2,6-diisocyanatohexanoate, ethyl
  • Examples of monomeric alicyclic polyisocyanates carrying two NCO groups 1 ,4-diisocyanato- cyclohexane, 1 ,3-diisocyanatocyclohexane, 1 ,2-diisocyanatocyclohexane, 4,4’- di(isocyanato- cyclohexyl)methane, 2,4’-di(isocyanatocyclohexyl)methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl)cyclohexane (isophorone diisocyanate), 1 ,3- bis(isocyanatomethyl)- cyclohexane, 1 ,4-bis(isocyanatomethyl)cyclohexane, 2,4- diisocyanato-1 -methylcyclohexane,
  • Examples of monomeric aromatic polyisocyanates carrying two NCO groups are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 2,4’- diisocyanatodiphenylmethane, 4,4’-diisocyanatodiphenylmethane, 1 ,3-phenylene diisocyanate, 1 ,4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1 ,5-naphthylene diisocyanate, diphenylene 4,4’-diisocyanate, 4,4’-diisocyanato-3,3’-dimethylbiphenyl, 3-methyl- diphenylmethane 4,4’-diisocyanate, tetramethylxylylene diisocyanate, 1 ,4-diisocyanato
  • Examples of monomeric aliphatic polyisocyanates carrying at least three NCO groups are 1 ,4,8- triisocyanatononane, 2’-isocyanatoethyl 2,6-diisocyanatohexanoate.
  • Examples of monomeric aromatic polyisocyanates carrying at least three NCIO groups are 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate and 2,4,4’-triisocyanatodiphenyl ether.
  • Monomeric polyisocyanates can be prepared by methods known in the art, for example by treating the corresponding amines with phosgene.
  • the polymeric polyisocyanate usually comprises at least one unit derived from monomeric polyisocyanate.
  • the polymeric polyisocyanate preferably comprises (i) at least one unit independently derived from the group consisting of monomeric aliphatic, alicylic and aromatic polyisocyanates, and (ii) at least one structural unit selected from the group consisting of uretdione, isocyanurate, biuret, urea, carbodiimide, uretonimine, urethane, allophanate, oxadiazinetrione and iminooxadiazinedione.
  • the NCO content of polymeric polyisocyanates is usually in the range of 5 to 40 % (weight NCO groups based on the weight of the polymeric polyisocyanate).
  • the polyisocyanate (2v) is preferably an aliphatic or alicyclic polyisocyanate, more preferably an alicyclic polyisocyanate, even more preferably a monomeric alicyclic diisocyanate, and most preferably 1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane (isophorone diisocyanate).
  • the polyamine (2vi) carrying at least two amino groups independently selected from the group consisting of primary and secondary amino groups can carry further functional group such as OH groups and acidic groups or salts thereof. Examples of acidic groups and salts thereof are given above.
  • the polyamine (2vi) can be an aliphatic, alicyclic or aromatic polyamine carrying at least two amino groups independently selected from the group consisting of primary and secondary amino group.
  • Aromatic polyamines carrying at least two amino groups independently selected from the group consisting of primary and secondary amino groups are polyamines, wherein at least one primary or secondary amino group is directly attached to an aromatic ring.
  • Alicyclic polyamines carrying at least two amino groups independently selected from the group consisting of primary and secondary amino groups comprise at least one alicyclic ring and each primary or secondary amino group is not directly attached to an aromatic ring.
  • Aliphatic polyamines carrying at least two amino groups independently selected from the group consisting of primary and secondary amino groups do not comprise an alicyclic ring and each primary or secondary amino group is not directly attached to an aromatic ring.
  • Preferred aliphatic and alicyclic polyamines carrying at least two amino groups independently selected from the group consisting primary and secondary amino groups do not comprise aromatic rings.
  • Examples of aliphatic polyamines carrying at least two amino groups independently selected from the group consisting of primary and secondary amino groups are ethylenediamine, propylenediamine, butylenediamine, neopentanediamine, hexamethylenediamine, 4,9-dioxado- decane-1 ,12-diamine, 4,7,10-trioxatridecane-1 ,13-diamine, 3-(methylamino)propylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, piperazine, 2-(2-aminoethylamino)- ethanol, 2-(2-aminoethylamino)ethanol, 6-amino-4-azahexanecarboxylic acid (N-(2'-carboxy- ethyl)ethylenediamine) or salts thereof and 5-amino-3-azapentanesulfonic acid (N-(2'-sulfo- ethyl
  • Examples of alicyclic polyamines carrying at least two amino groups independently selected from the group consisting of primary and secondary amino groups are 4,4’-diaminodicyclo- hexylmethane and isophorone diamine.
  • the polyamine (2vi) carrying at least two amino groups independently selected from the group consisting of primary and secondary amino groups is preferably an aliphatic or alicyclic polyamine carrying at least two amino groups independently selected from the group consisting of primary and secondary amino groups, more preferably an aliphatic or alicyclic polyamine carrying at least two amino groups independently selected from the group consisting of primary and secondary amino groups, which do not carry further functional groups, and most preferably diethylenetriamine, isophorone diamine or mixtures thereof.
  • the compound (2vii) carrying at least one olefinically unsaturated group and no NCO reactive group can be a compound carrying one olefinically unsaturated group and no NCO reactive group or a compound carrying at least two olefinically unsaturated groups and no NCO reactive group
  • Examples of compounds carrying one ethylenically unsaturated group and no NCO reactive group are (meth)acrylic-type monomers carrying only one ethylenically unsaturated group and no NCO reactive group and styrene-type monomers carrying only one ethylenically unsaturated group and no NCO reactive group.
  • (Meth)acrylate include methacrylate and acrylate.
  • (Meth)acrylamide includes methacrylamide and acrylamide.
  • Ci-2o-alkyl(meth)acrylate examples include methyl(meth)acrylate, ethyl(meth)acrylate, n- propyl(meth)acrylate, butyl(meth)acrylate, isobutyl(methacrylate), sec-butyl(meth)acrylate, tert- butyl(meth)acrylate, pentyl(meth)acrylate, isopentyl(meth)acrylate, 2-methylbutyl(meth)acrylate, amyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylbutyl(meth)acrylate, heptyl(methacrylate, octyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, 2-propylheptyl(meth)acrylate, nony(meth)acrylate), decyl(methacrylate), undecyl(meth)acrylate and do
  • Examples of [Ci-io-alkoxy(Ci-io-alkoxy)o-5]Ci-io-alkyl(methacrylate) are 2-methoxyethyl- (meth)acrylate,2-ethoxyethyl(meth)acrylate, 4-methoxybutyl(meth)acrylate, 2-(2’-methoxy- ethoxy)ethyl(meth)acrylate.
  • C5-i2-cycloalkyl(meth) acrylate examples include cyclopentyl(meth)acrylate and cyclohex- yl(meth)acrylate.
  • styrene-type monomers examples include styrene, alpha-methylstyrene, para-methylstyrene, alpha-butylstyrene, para-butylstyrene and 2-vinylnaphthalene.
  • Examples of compounds carrying at least two olefinically unsaturated group and no NCO reactive group are (meth)acrylic-type monomers carrying at least two ethylenically unsaturated group and no NCO reactive group, and styrene-type monomers carrying at least two ethylenically unsaturated group and no NCO reactive group.
  • Examples of (meth)acrylic-type monomers carrying at least two ethylenically unsaturated group and no NCO reactive group are allyl (meth)acrylate, methallyl (meth)acrylate, 1 ,2-ethyleneglycol di(meth)acrylate, 1 ,2-propyleneglycol di(meth)acrylate, 1 ,3-propyleneglycol di(meth)acrylate, 1 ,2-butanediol di(meth)acrylate, 1 ,3-butanediol-di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, neopentylglycol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, 1 ,9-nonanediol di(meth)acrylate, 1 ,10-decanediol di (methacrylate), diethyleneglycol di
  • An example of a styrene-type monomer carrying at least two ethylenically unsaturated group and no NCO reactive group is divinylbenzene.
  • Ci-2o-alkylene can be branched or unbranched.
  • Examples of Ci-2o-alkylene are Ci-w-alkylene and undecylene, dodecylene, tridecylene and hexadecylende.
  • Examples of Ci-w-alkylene are given above.
  • Examples of C2-6-alkylene are ethylene, propylene, buylene, pentylene and hexylene.
  • the organic solvent (4) can be an aliphatic ketone such as acetone, ethyl methylketone or isobutyl methyl ketone, an aliphatic amide such as N-methylpyrrolidone or N-ethylpyrrolidone, an ether such as tetrahydrofuran, dipropylene glycol dimethyl ether or dioxane, a hydrocarbon such as n-heptane, cyclohexane, toluene, ortho-xylene, meta-xylene, para-xylene, and xylene isomer mixture, an ester such as butyl acetate, an acid such as acetic acid or a nitrile such as acetonitrile, or a mixture thereof.
  • an aliphatic ketone such as acetone, ethyl methylketone or isobutyl methyl ketone
  • an aliphatic amide such as N-methylpyrroli
  • the organic solvent (4) is preferably an aliphatic ketone, more preferably acetone, ethylmethylketone or a mixture thereof.
  • the first step is usually performed at a temperature in the range of from 50 to 150 °C, more preferably in the range of 70 °C to 110 °C.
  • the reaction time is usually between 30 minutes and 10 hours.
  • the first step is preferably performed in the presence of a catalyst.
  • Examples of catalysts are amine catalysts carrying at least one tertiary amino group and organ- ometal catalysts.
  • amine catalysts carrying at least one tertiary amino group are 1 ,4-diazabicyclo- [2.2.2]octane, N-methylmorpholine, N-methylimidazole, bis[2-(N,N-dimethylamino)ethyl] ether, 2,2’-dimorpholinyldiethylether and tetramethylethylenediamine, dimethylcyclohexylamine, dimethylbenzylamine, dimethylethanolamine and dimethylaminopropyl amine.
  • a preferred amine catalysts carrying at least one tertiary amino group areis 1 ,4-diazabicyclo[2.2.2]octane.
  • organometallic catalysts examples include organo titanium catalysts, organo tin catalysts, organo zinc catalysts, organo bismuth catalysts, organo zirconium catalysts, organo iron catalysts, organo aluminum catalysts, organo manganese catalysts, organium nickel catalysts, organo cobalt catalysts, organo molybdenum catalysts, organo tungsten catalysts and organo vanadium catalysts.
  • the organo titanium catalysts can be titanium(IV) tetra(Ci-io-alkoxide), and preferably titanium (IV) tetra(Ci-6-alkoxide).
  • Ci-6-alkoxide and Ci- -alkoxide can be branched or unbranched. Examples of Ci-6-alkoxide are methoxide, ethoxide, propoxide, isipropoxide, butoxide, isobutox- ide, sec-butoxide, terf-butoxide, pentoxide, hexoxide.
  • Ci-w-alkoxide examples are methoxide, ethoxide, propoxide, isipropoxide, butoxide, isobutoxide, sec-butoxide, terf-butoxide, pentoxide, hexoxide, heptoxide, octoxide, 2-ethylhexoxide, nonoxide, decoxide.
  • titanium(IV) tetra(Ci-4-alkoxide) are titanium(IV) tetra(isopropoxide) and titanium(IV) tetra(butoxide).
  • organo tin catalyst examples include tin(ll) di(C2-2o-alkanoates) such as tin(ll) diacetate, tin(ll) di(2-ethylhexanoate) and tin(ll) dilaurate, di(Ci-io-alkyl)tin(l V) di(C2-2o-alkanoates) such as dime- thyltin(IV) diacetate, dibutyltin(IV) diacetate, dibutyltin(l V)dibutyrate, dibutyltin di(2- ethyl hexanoate), dibutyltin(IV) dilaurate, dioctyltin(IV) dilaurate and dioctyltin(IV) diacetate, di(Ci-io-alkyl) tin(IV) oxide such as dibutyl tin(IV) oxide and diphenyl tin(
  • C2-io-alkanoates can be branched or unbranched.
  • Examples of C2-2o-alkanoates are acetate, propionate, butyrate, pentanoate, pivalate, hexanoate, heptanoate, octanoate, 2-ethylhexanoate (octoate), nonanoate, decanoate, neodecanoate and dodecanoate (laurate).
  • organo zinc catalyst examples include a zinc(ll) di(C2-2o-alkanoate) such as zinc(ll) diacetate, zinc(ll) di(2-ethylhexanoate) and zinc(ll) dineodecanoate.
  • organo bismuth catalyst examples include a bismuth(ll) di(C2-2o-alkanoate) such as bismith(ll) diacetate, bismuth(ll) dipivalate, bismuth(ll) di(2-ethylhexanoate) and bismuth(ll) dineodecanoate.
  • organo zirconium catalysts are zirconium(IV) tetra(acetylacetonate) and zirconium(IV) etrakis(2,2,6,6-tetramethyl-3,5-heptanedionate).
  • the catalyst is preferably an organometal catalyst, more preferably an organo titanium catalyst, even more preferably titanium(IV) tetra(Ci-6-alkoxide) and most preferably titanium(IV) tet- ra(butoxide).
  • the NCO content of the polyurethane prepolymer of the first step is usually in the range of 1.1 % to 1.5%.
  • the second step comprises the following “sub-steps”: optional addition of an organic solvent, treatment with at least one polyamine (2vi) carrying at least two amino groups independently selected from the group consisting of primary and secondary amino groups, treatment with at least one base to completely or partially convert the acidic groups derived from the polyol (2i iia) carrying at least one acidic group to the salt thereof, addition of water.
  • the “sub”-steps of the second step can be performed in any order, but preferably the sub-steps are performed in the indicated order.
  • the treatment with at least one polyamine (2vi) is usually performed at a temperature in the range of from 20 to 100 °C, more preferably in the range of 20 °C to 50 °C, most preferably in the range of from 20 to 40 °C.
  • the reaction time of the treatment with at least one polyamine carrying at least two amino groups independently selected from the group consisting of primary and secondary amino groups (2vi) is usually between 2 minutes and 1 hour.
  • the base can be an inorganic base, ammonia or an amine carrying only one amino group. Examples of inorganic base and of amine carrying only one amino group are given above.
  • the treatment with at least one base is usually performed at a temperature in the range of from 20 °C to 60 °C, most preferably in the range of from 20 to 40 °C.
  • the reaction time of the treatment with at least one base is usually between 1 minute and 1 hour.
  • any organic solvent present is usually removed by distillation.
  • the initiator of the fifth step can be any suitable initiator or a mixture thereof.
  • the initiator can be a peroxide-type initiator such as potassium peroxodisulate, sodium perox- odiulfate, ammonium peroxodisulfate, hydrogen peroxide and tert-butyl hydroperoxide, and mixtures thereof.
  • the initiator can be an azo-type initiator such as 2,2'-azobis(2-amidoisopropane)dihydro- chloride, 2,2'-azobis(N,N'-dimethyleneisobutyramidine)dihydrochlorideand 2,2'-azobis(4- cyanopentanoicacid), and mixtures thereof.
  • the initiator can be a redox initiator system-type initiator such as a combination of an oxidizing compound with a reducing compound.
  • oxidizing compounds are the peroxide-type initiators listed above.
  • reducing compounds are reducing sulfur compounds such as alkali metal or ammonium bisulfites, sulfites, thiosulfates, dithionites or tetra-thionates, as well as alkali metal hydroxymethanesulfinate dihydrates and thiourea.
  • An example of a redox initiator initiator system type initiator is the combination of ammonium peroxodisulfate and ammonium disulfite.
  • the weight ratio of oxidizing compound to the reducing compound is preferably 50:1 to 0.05:1.
  • the peroxide-type initiators, the azo-type initiators and the redox initiator sytem-type initiators can be combined with a transition metal catalysts, for example iron salts, nickel salts, cobalt salts, manganese salts, copper salts, vanadium salts, chromium salts, such as iron(ll) sulfate, cobalt(ll) chloride, nickel(ll) sulfate, copper(l) chloride, manganese(ll) acetate, vanadi- um(lll) acetate, manganese(ll) chloride.
  • a transition metal catalysts for example iron salts, nickel salts, cobalt salts, manganese salts, copper salts, vanadium salts, chromium salts, such as iron(ll) sulfate, cobalt(ll) chloride, nickel(ll) sulfate, copper(l) chloride, manganese(ll) acetate, vanadi- um(
  • the peroxide-type initiators, the azo-type initiators and the redox initiator sytem-type initiators are preferably used in an amount of 0.05 to 20 weight%, preferably 0.05 to 10 weight%, more prefer-ably 0.1 to 5 weight%, based on the total weight of the compound carrying at least one olefinically unsaturated group and no NCO reactive groups (2vii).
  • the transition metal salts, if present, are typically used in amounts of 0.1 to 1000 ppm.
  • the polymerization of the fifth step is usually performed at a temperature in the range of from 0 to 160 °C, preferably in the range of from 60 to 100 °C.
  • SC-PUD a process for the preparation of the aqueous self- crosslinkable polyurethane dispersion
  • an aqueous self-crosslinkable polyurethane coating composition comprising the aqueous self-crosslinkable polyurethane dispersion (SC-PUD) of the present invention, optionally at least an organic solvent (5), at least one coating composition additive (6), optionally at least one polymer (7) different from the polyurethane (2), and optionally at least one monomer (8) carrying at least one olefinically unsaturated group.
  • the aqueous self-crosslinkable polyurethane coating composition of the present invention comprises
  • SC-PUD aqueous self-crosslinkable polyurethane dispersion
  • At least one monomer (8) carrying at least one olefinically unsaturated group based on the weight of aqueous self-crosslinkable polyurethane dispersion of the present invention, (5), (6), (7) and (8).
  • the aqueous self-crosslinkable polyurethane coating composition of the present invention comprises
  • SC-PUD aqueous self-crosslinkable polyurethane dispersion
  • At least one monomer (8) carrying at least one olefinically unsaturated group based on the weight of aqueous self-crosslinkable polyurethane dispersion of the present invention, (5), (6), (7) and (8).
  • the aqueous self-crosslinkable polyurethane coating composition of the present invention comprises
  • At least one monomer (8) carrying at least one olefinically unsaturated group based on the weight of aqueous self-crosslinkable polyurethane dispersion of the present invention, (5), (6), (7) and (8).
  • organic solvent (5) examples include glycol ether, alcohols, esters and hydrocarbons.
  • glycol ether examples include ethylene glycol monomethyl ether, diethylene glycol monomethylether, diethylene glycol monom butyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether, ethyleneglycol dimethyl ether and ethyleneglycol diethylether, ethylene glycol methyl ether actate and propyleneglycol methyl ether acetate.
  • Examples of alcohols are benzyl alcohol, butanol, 2-ethyl-hexanol.
  • esters are methyl acetate, ethyl acetate and butyl acetate.
  • Examples of hydrocarbons are white spirit, n- heptane, cyclohexane, toluene, ortho-xylene, meta-xylene, para-xylene, and xylene isomer
  • the organic solvent (5) is preferably a glycol ether.
  • coating composition additive (6) examples include matting agents, nanoparticles, dispersants, thickening agents, wetting agents, surface active components like emulsifiers, defoamers, pigments and pigment pastes.
  • An example of a matting agent is AcemattOTS 100 (pyrogenic silicic acid).
  • hydropalat® WE 3221 An example of a wetting agent is Hydropalat® WE 3221.
  • FoamStar® ST 2454 An example of a defoamer is FoamStar® ST 2454.
  • Examples of monomer (8) carrying at least one olefinically unsaturated group are the compounds (2vii) carrying at least one olefinically unsaturated groups and no NCO reactive group, and the alcohols or polyols (2iv) carrying at least one ethylenically unsaturated group.
  • the compounds (2vii) and (2iv) are described above.
  • the monomers (7) are compounds carrying at least two olefinically unsaturated groups and no NCO reactive group, and alcohols or polyols carrying at least two ethylenically unsaturated groups. Examples of these compounds are given above.
  • the aqueous self-crosslinkable polyurethane coating composition of the present invention can be prepared by mixing the ingedients, usually at room temperature.
  • the pH of the aqueous self- crosslinkable coating composition of the present invention can be adjusted when necessary.
  • the pH is adjusted to a pH of 6 to 10, more preferably to a pH of 7 to 9.
  • Also part of the present invention are substrates coated with the aqueous self-crosslinkable polyurethane coating composition of the present invention.
  • the substrate can be any suitable substrates.
  • the substrate can be wood, plastic, metal, paper, glass, textiles, leather, fiber reinforced composites and mixtures thereof.
  • the substrate can have the form of housings and other structural parts used to build vehicels, for example automobiles or used in all types of industrial and domestic applications.
  • the substrate is preferably wood, more preferably wood used in interior application such as parquet flooring.
  • Also part of the present invention is a process for coating a substrate, which comprises the step of applying the aqueous self-crosslinkable polyurethane coating composition of the present invention to a substrate.
  • aqueous self-crosslinkable coating composition of the present invention can be applied to the substrate by any method known in the art, for example by using a film applicator, to form a layer.
  • the layer usually has a thickness in the range od 100 to 150 .m.
  • the layer usually is applied and allowed to cross-link at a temperature in the range of 5 to 40 °C and at a relative humidity in the range of 10 to 90%.
  • the layer is applied and allowed to cross-link at a temperature in the range of 5 to 20 °C, preferably 8 to 18°C, and at a relative humidity in the range of 45 to 85%.
  • the aqueous self-crosslinkable polyurethane coating compositions of the present invention are advantageous in that the compositions are able to crosslink under various conditions with regard to temperature and relative humidity to form a homogenous crack-free film.
  • the aqueous self-crosslinkable polyurethane coating compositions of the present invention are not only able to crosslink under ambient conditions, such as at temperatures in the range of 20 to 23 °C and at relative humidities in the range of 20% to 50%, but also under conditions where the temperatures are low, such as in the range of 10 to 17 °C, and, at the same time, the relative humidity is high, such as in the range of 50 to 80%.
  • aqueous self-crosslinkable polyurethane coating compositions of the present invention are also advantageous in that the formed films are resistant against water treatment for 24 hours.
  • aqueous self-crosslinkable polyurethane coating compositions of the present invention are also advantageous in that no external cross-linker is required.
  • aqueous self-crosslinkable polyurethane coating compositions of the present invention are also advantageous in that the compositions contain only a low amount of organic solvent, preferably maximum 10 weight%, more preferably maximum 8 weight%, most preferably maximum 5 weight% of an organic solvent based on the weight of the composition.
  • aqueous self-crosslinkable polyurethane coating compositions of the present invention are also storage stable, fast drying, show a high chemical resistance, high abrasion resistance, and/or a high final hardness.
  • aqueous self-crosslinkable polyurethane coating compositions of the present invention also shows a high resistance against organic solvents such as acetone and ethanol.
  • a mixture of 36.45 kg levulinic acid and 23.64 kg 1 ,4-cyclohexane dimethanol (cis/trans mixture) was melted at 60 °C. 50.98 kg adipic acid and 39.33 kg trimethylolpropane were added and the reaction mixture was heated under stirring and inert atmosphere at 100 °C until a clear solution was obtained (approximately 4 hours).
  • a solution of 0.045 kg titanium (IV) butoxide in 500 mL methylethylketone was added. The reaction mixture was heated under stirring to 160 °C and kept for 3 hours at this temperature.
  • SC-PUD2a aqueous self-crosslinkable polyurethane dispersion
  • ADDH adipic acid dihydrazide
  • DMPA dimethylolpropionic acid
  • 100 g of polyester polyol 1a of example 1 , 74.8 g 1 ,4-butandiol and 100 g acetone were mixed at 65 °C. 366.3 g isophorone diisocyanate was added, the temperature was increased to 90 °C, and the reaction mixture was allowed to react for 2 hours. The mixture was diluted with 790 g acetone, and the NCO content was measured (1.46%).
  • IPDA isophorone diamine
  • DEEA diethanolethylamine
  • 1400 g Water was added to the reaction mixture under rapid stirring to obtain a dispersion of the polyurethane in water.
  • 10.5 g diethylenetriamine (DETA) was added and the reaction mixture was allowed to react for 15 min. Acetone was removed by distillation.
  • adipic acid dihydrazide (12 wt% ADDH in water) was added to the dispersion to obtain an aqueous seld-crosslinkable polyurethane dispersion (SC- PUD2a) comprising polyurethane 2a and adipic acid dihydrazide (ADDH) (3a) (solid content: 37 wt%, viscosity at 23 °C: 80 -200 mPas, pH: 7.5-8.5, minimum film forming temperature: 19°C, particle size: 100 nm).
  • SC- PUD2a aqueous seld-crosslinkable polyurethane dispersion
  • SC- PUD2a aqueous seld-crosslinkable polyurethane dispersion
  • solid content 37 wt%, viscosity at 23 °C: 80 -200 mPas, pH: 7.5-8.5, minimum film forming temperature: 19°C, particle size: 100 nm).
  • DMPA dimethylolpropionic acid
  • 100 g of polyester polyol 1a of example 1 73,35 g 1,4-butandiol and 100 g acetone were mixed at 65 °C.
  • 356,31 g isophorone diisocyanate was added, the temperature was increased to 90 °C, and the reaction mixture was allowed to react for 2 hours .
  • the mixture was diluted with 800 g acetone, and the NCO content was measured (1.27%).
  • IPDA isophorone diamine
  • DEEA diethanolethylamine
  • 1600 g Water was added to the reaction mixture under rapid stirring to obtain a dispersion of the polyurethane in water.
  • DETA diethylenetriamine
  • adipic acid dihydrazide (12 wt% ADDH in water) was added to the dispersion to obtain an aqueous self-crosslinkable polyurethane dispersion (SC-PUD2b) comprising polyurethane 2b and adipic acid dihydrazide (ADDH) (3a) (solid content: 37 wt%, viscosity at 23 °C: 80-200 mPas, pH: 7.5-8.5, minimum film forming temperature: 15-17°C, particle size- 100 nm).
  • SC-PUD2b aqueous self-crosslinkable polyurethane dispersion
  • ADH adipic acid dihydrazide
  • DMPA dimethylolpropionic acid
  • 100 g of the polyester polyol 1a of example 1 , 72.0 g 1 ,4-butandiol and 100 g acetone were mixed at 65 °C.
  • 346,6 g isophorone diisocyanate was added, the temperature was increased to 90 °C, and the reaction mixture was allowed to react for 2 hours.
  • the mixture was diluted with 800 g acetone, and the NCO content was measured (1.16%).
  • IPDA isophorone diamine
  • DEEA diethanolethylamine
  • 1600 g Water was added to the reaction mixture under rapid stirring to obtain a dispersion of the polyurethane in water. 7.75 g diethylenetriamine (DETA) was added and the reaction mixture was allowed to react for 15 min. Acetone was removed by distillation.
  • adipic acid dihydrazide (12 wt% ADDH in water) was added to the dispersion to obtain an aqueous self-crosslinkable polyurethane dispersion (SC-PUD2c) comprising keto polyurethane 2c and adipic acid dihydrazide (ADDH) (solid content: 37 wt%, viscosity at 23 °C: 80-200 mPas, pH: 7.5-8.5, minimum film forming temperature: 11-14°C, particle size- 100 nm).
  • SC-PUD2c aqueous self-crosslinkable polyurethane dispersion
  • ADH adipic acid dihydrazide
  • matting coating compositions comprising the aqueous self-crosslinkable polyure- thane dispersions SC-PUD2a, SC-PUD2b and SC-PUD2c of examples 2, 3 and 4, respectively, and 5 weight % organic solvent mixture DowanolTMDpnB/ DowanolTM DPM in a weight ratio 4/1
  • DMEA N,N-dimethylaminoethanol
  • AcemattOTS 100 pyrogenic silicic acid
  • DowanolTM DpnB slow-evaporating, hydrophobic glycol ether
  • DowanolTM DPM diprop
  • a comparative matting coating composition was prepared in analogy to the matting coating compositions of example 5, but using NeoRez® R-2180 (DSM Coating Resins LLC, aliphatic, self-cross-linking, water-based polyurethane, acid value: 0, solid content: 38.0 wt%, viscosity at 23 °C: 25-150 mPas, pH: 7.4-8.4) instead of SC-PUD2a, SC-PUD2b and SC-PUD2c of examples 2, 3 and 4, respectively.
  • NeoRez® R-2180 DSM Coating Resins LLC, aliphatic, self-cross-linking, water-based polyurethane, acid value: 0, solid content: 38.0 wt%, viscosity at 23 °C: 25-150 mPas, pH: 7.4-8.4
  • a matting coating composition comprising the aqueous self-crosslinkable polyurethane dispersions SC-PUD2a, SC-PUD2b and SC-PUD2c of examples 2, 3 and 4, respectively, and 3 weight % organic solvent organic solvent mixture DowanolTMDpnB/ DowanolTM DPM in a weight ratio 4/1
  • DMEA N,N-dimethylaminoethanol
  • Acematt®TS 100 pyrogenic silicic acid
  • DowanolTM DpnB slow-evaporating, hydrophobic glycol ether
  • DowanolTM DPM diprop
  • a comparative matting coating composition was prepared in analogy to the matting coating compositions of example 6, but using NeoRez® R-2180 (DSM Coating Resins LLC, aliphatic, self-cross-linking, water-based polyurethane, acid value: 0, solid content: 38.0 wt%, viscosity at 23 °C: 25-150 mPas, pH: 7.4-8.4) instead of SC-PUD2a, SC-PUD2b and SC-PUD2c of exam- ples 2, 3 and 4, respectively.
  • NeoRez® R-2180 DSM Coating Resins LLC, aliphatic, self-cross-linking, water-based polyurethane, acid value: 0, solid content: 38.0 wt%, viscosity at 23 °C: 25-150 mPas, pH: 7.4-8.4
  • matting coating compositions comprising the aqueous self-crosslinkable polyurethane dispersions SC-PUD2a, SC-PUD2b and SC-PUD2c of examples 2, 3 and 4, respectively, and 5 weight % organic solvent mixture DowanolTMDpnB/ DowanolTM DPM in a weight ratio 1/4
  • DMEA N,N-dimethylaminoethanol
  • AcemattOTS 100 pyrogenic silicic acid
  • DowanolTMDpnB slow-evaporating, hydrophobic glycol ether
  • DowanolTM DPM diprop
  • a comparative matting coating composition was prepared in analogy to the matting coating compositions of example 7, but using NeoRez® R-2180 (DSM Coating Resins LLC, aliphatic, self-cross-linking, water-based polyurethane, acid value: 0, solid content: 38.0 wt%, viscosity at 23 °C: 25-150 mPas, pH: 7.4-8.4) instead of SC-PUD2a, SC-PUD2b and SC-PUD2c of examples 2, 3 and 4, respectively.
  • NeoRez® R-2180 DSM Coating Resins LLC, aliphatic, self-cross-linking, water-based polyurethane, acid value: 0, solid content: 38.0 wt%, viscosity at 23 °C: 25-150 mPas, pH: 7.4-8.4
  • matting coating compositions comprising the aqueous self-crosslinkable polyurethane dispersions SC-PUD2a, SC-PUD2b and SC-PUD2c of examples 2, 3 and 4, respectively, and 3 weight % organic solvent mixture DowanolTMDpnB/ DowanolTM DPM in a weight ratio 1/4
  • DMEA N,N-dimethylaminoethanol
  • Acematt®TS 100 pyrogenic silicic acid
  • DowanolTM DpnB slow-evaporating, hydrophobic glycol ether
  • a comparative matting coating composition was prepared in analogy to the matting coating de compositions of example 8, but using NeoRez® R-2180 (DSM Coating Resins LLC, aliphatic, self-cross-linking, water-based polyurethane, acid value: 0, solid content: 38.0 wt%, viscosity at 23 °C: 25-150 mPas, pH: 7.4-8.4) instead of SC-PUD2a, SC-PUD2b and SC-PUD2c of examples 2, 3 and 4, respectively.
  • NeoRez® R-2180 DSM Coating Resins LLC, aliphatic, self-cross-linking, water-based polyurethane, acid value: 0, solid content: 38.0 wt%, viscosity at 23 °C: 25-150 mPas, pH: 7.4-8.4
  • parquet wood board samples (30 x 15 cm) were polished using sandpaper (grain size 150).
  • 1.8 g of a wood stain (Loba ProColor, 900005 Black, Lobadur) was applied on the surface of each wood board sample using a metal spatula.
  • the wood board samples were allowed to dry over the weekend at room temperature (approximately 60 hours).
  • coated wood board samples were then conditioned under the conditions described in tables 1 and 2 for 24 hours before the matting coating compositions were applied.
  • the matting coating compositions were applied on the wood board samples using a film applicator to yield a 120 .m thick film, which was allowed to dry for 5 hours under the conditions described in tables 1 and 2. Then, the matting coating compositions were applied a second time to yield a new 120 .m thick film, which was allowed to dry overnight (approximately 12 h), again under the conditions described in tables 1 and 2
  • the surface of wood board samples was polished lightly using sandpaper (grain size 150), and the matting coating compositions were applied a third time to yield a new 120 .m thick film, which was allowed to dry for 7 days, again under the conditions described in tables 1 and 2.
  • the coated wood board samples were treated with water for 24 hours in laboratory atmosphere, and the coating layer formed from the matting coating compositions was analyzed directly after the water treatment by visual inspection.
  • the film formation behaviour of the coating compositions was ranked from score 1 (worst film formation) to score 5 (best film formation).
  • Table 1 shows that the film formation behavior at temperatures from 21 to 23 °C and at 20 to 50% relative humidities, and after 24 h water treatment of the dryed film, of the inventive coating compositions of example 5 comprising the aqueous self-crosslinkable polyurethane dispersions SC-PUD2a, SC-PUD2b and SC-PUD2c of examples 2, 3 and 4, respectively, and 5 weight% organic solvent mixture DowanolTMDpnB/ DowanolTM DPM in a weight ratio 4/1 is ranked with the highest score (score 5) and is comparable to the film forming behavior of comparative coating composition of comparative example 5 comprising the aqueous dispersion NeoRez® R- 2180 (DSM Coating Resins LLC).
  • Table 1 shows that the film formation behavior at temperatures from 10 to 17 °C and at 50 to 80% relative humidities, and after 24 h water treatment of the dryed film, of the inventive coating compositions of example 5 comprising the aqueous self-crosslinkable polyurethane dispersions SC-PUD2a, SC-PUD2b and SC-PUD2c of examples 2, 3 and 4, respectively, and 5 weight % organic solvent mixture DowanolTMDpnB/ DowanolTM DPM in a weight ratio 4/1 is ranked with the highest score (score 5) and is better than the film forming behavior of comparative coating composition of comparative example 5 comprising the aqueous dispersion NeoRez® R-2180 (DSM Coating Resins LLC).
  • Table 1 also shows that the film formation behaviour at temperatures from 10 to 17 °C and at 50 to 80% relative humidities, and after 24 h water treatment of the dryed film, of the inventive coating compositions of example 6 comprising the aqueous self-crosslinkable polyurethane dispersions SC-PUD2a, SC-PUD2b and SC-PUD2c of examples 2, 3 and 4, respectively, and only 3 weight % organic solvent mixture DowanolTMDpnB/ DowanolTM DPM in a weight ratio 4/1 is slightly worse than that of the inventive coating compositions of example 5 comprising 5 weight% organic solvent, but much better than that of comparative coating composition of comparative example 6 comprising the aqueous dispersion NeoRez® R-2180 (DSM Coating Resins LLC) and 3 weight% organic solvent.
  • the scores for the coating compositions of examples 7 and 8 and comparative examples 7 and 8 are summarized in table 2.
  • Table 2 shows that the film formation behavior at temperatures from 10 to 17 °C and at 50 to 80% relative humidities, and after 24 h water treatment of the dryed film, of the inventive coating compositions of example 7 comprising the aqueous self-crosslinkable polyurethane dispersions SC-PUD2a, SC-PUD2b and SC-PUD2c of examples 2, 3 and 4, respectively, and 5 weight% organic solvent mixture DowanolTMDpnB/ DowanolTM DPM in a weight ratio 1/4 is ranked with the highest score (score 5) and is better than the film forming behavior of comparative coating composition of comparative example 7 comprising the aqueous dispersion NeoRez® R-2180 (DSM Coating Resins LLC).
  • Table 2 also shows that the film formation behaviour at temperatures from 10 to 17 °C and at 50 to 80% relative humidities, and after 24 h water treatment of the dryed film, of the inventive coating compositions of example 8 comprising the aqueous self-crosslinkable polyurethane dispersions SC-PUD2a, SC-PUD2b and SC-PUD2c of examples 2, 3 and 4, respectively, and only 3 weight % organic solvent mixture DowanolTMDpnB/ DowanolTM DPM in a weight ratio 1/4 is slightly worse than that of the inventive coating compositions of example 7 comprising 5 weight% organic solvent, but much better than that of comparative coating composition of comparative example 8 comprising the aqueous dispersion NeoRez® R-2180 (DSM Coating Resins LLC) and 3 weight% organic solvent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP21778371.1A 2020-09-25 2021-09-14 Wässrige selbstvernetzbare polyurethandispersionen Pending EP4217410A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20198518 2020-09-25
PCT/EP2021/075208 WO2022063638A1 (en) 2020-09-25 2021-09-14 Aqueous self-crosslinkable polyurethane dispersions

Publications (1)

Publication Number Publication Date
EP4217410A1 true EP4217410A1 (de) 2023-08-02

Family

ID=72659707

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21778371.1A Pending EP4217410A1 (de) 2020-09-25 2021-09-14 Wässrige selbstvernetzbare polyurethandispersionen

Country Status (4)

Country Link
US (1) US20230374192A1 (de)
EP (1) EP4217410A1 (de)
CN (1) CN116323737A (de)
WO (1) WO2022063638A1 (de)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8904102D0 (en) 1988-03-09 1989-04-05 Ici Resins Bv Polyurethane coating compositions
DE3837519A1 (de) 1988-11-04 1990-05-10 Basf Lacke & Farben Lagerstabile vernetzbare waessrige polyurethandispersionen
AT500555B1 (de) 2003-06-13 2009-11-15 Cytec Surface Specialties At Selbstvernetzende wässrige polyurethandispersionen
KR101323814B1 (ko) 2005-02-07 2013-11-01 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 폴리우레탄 조성물의 수성 분산액
US7576157B2 (en) 2006-07-31 2009-08-18 Lubrizol Advanced Materials, Inc. Aqueous dispersions of polyurethane compositions with ketone-hydrazide
JP5649978B2 (ja) 2008-02-19 2015-01-07 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド エポキシ化天然油から得られる水性ポリマー組成物
BR112013010073A2 (pt) * 2010-11-11 2016-07-05 Segetis Inc adutos de éster polihidróxi cetálico, métodos de fabricação e seus usos
US20150079406A1 (en) 2012-04-10 2015-03-19 Dsm Ip Assets B.V. Polymer, composition and use
CN104418983A (zh) 2013-08-26 2015-03-18 广东华润涂料有限公司 可自交联的聚合物以及含有这种聚合物的颗粒的水性分散体
EP3712190A1 (de) * 2019-03-18 2020-09-23 ALLNEX AUSTRIA GmbH Bindemittel für eine wässrige beschichtungszusammensetzung

Also Published As

Publication number Publication date
WO2022063638A1 (en) 2022-03-31
CN116323737A (zh) 2023-06-23
US20230374192A1 (en) 2023-11-23

Similar Documents

Publication Publication Date Title
DE60129319T2 (de) Wässrige vernetzbare bindemittelzusammensetzung und beschichtungs-, lack- oder dichtmittelzusammensetzung, die diese bindemittelzusammensetzung beinhaltet
US9574089B2 (en) Fluorine-containing nonaqueous coating material composition, coating methods, and the use of the coating material composition
US5023294A (en) Aqueous dispersions of urethane-acrylic polymers and the use thereof as paints
EP1924624B1 (de) Wässrige 2k-pur systeme enthaltend hydroxy-funktionelle polydimethylsiloxane
US20060148980A1 (en) Waterborne self-crosslinkable polyurethane dispersions and polyurethane:acrylic hybrid dispersions
US9540477B2 (en) Radiation curable compositions
EP1328565A1 (de) Photoaktivierbare wässrige beschichtungszusammensetzungen
AU2002210574A1 (en) Photoactivatable water borne coating composition
DE102006049764A1 (de) UV-härtbare Polyurethan-Dispersionen
CN110300771B (zh) 水性涂料组合物
US20140323638A1 (en) Process for preparing polyurethane acrylic hybrid dispersions
CN108883432B (zh) 多层涂膜形成方法
AU747613B2 (en) Low VOC, isocyanate based aqueous curable compositions
CN111868133A (zh) 脲二酮分散体的催化剂体系
WO1998038230A9 (en) Low voc, isocyanate based aqueous curable compositions
WO2022063638A1 (en) Aqueous self-crosslinkable polyurethane dispersions
EP4263654A1 (de) Polyesterpolyole mit 2,5-bis(hydroxymethyl)tetrahydrofuran
WO2022069563A1 (en) Water-dispersible modified polyisocyanates
JPH11100528A (ja) 活性エネルギー線硬化性水性組成物
KR20010078333A (ko) 지환족 알칸디올로부터 유도된 알로파네이트기가 있는폴리이소시아네이트
KR100534503B1 (ko) 유화 중합체의제조방법 및 유화 중합체를 이용한 수성 도료용 수지 조성물
US20240191018A1 (en) Aqueous polyurethane and polyurethane/poly(meth)acrylate hybrid dispersions
WO2022129139A1 (en) Polyester polyols comprising isosorbide, isoidide or isomannide-derived units
CN117265888A (zh) 一种水性聚氨酯多层结构涂层及其制备方法
EP4400523A1 (de) Wässrige polyurethan-vinylpolymer-hybriddispersion

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20230425

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

TPAC Observations filed by third parties

Free format text: ORIGINAL CODE: EPIDOSNTIPA

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)